Search Results (3,168)

This review outlines a comprehensive methodology for the research and development of heterogeneous catalytic technologies (R&D_HeCaTe). Emphasis is placed on the fundamental interactions between reactants, solvents, and heterogeneous catalysts—specifically the roles of catalytic centers and support materials (e.g., functional groups) in modulating activation energies and stabilizing catalytic functionality. Particular attention is given to catalyst deactivation mechanisms and potential regeneration strategies. The application of molecular modeling and chemical engineering analyses, including reaction kinetics, thermal effects, and mass and heat transport phenomena, is identified as essential for R&D_HeCaTe. Reactor configuration is discussed in relation to key physicochemical parameters such as molecular diffusivity, reaction exothermicity, operating temperature and pressure, and the phase and “aggressiveness” of the reaction system. Suitable reactor types—such as suspension reactors, fixed-bed reactors, and flow microreactors—are evaluated accordingly. Economic and environmental considerations are also addressed, with a focus on the complexity of reactions, selectivity versus conversion trade-offs, catalyst disposal, and separation challenges. To illustrate the breadth and applicability of the proposed framework, representative industrial processes are discussed, including ammonia synthesis, fluid catalytic cracking, methanol production, alkyl tert-butyl ethers, and aniline. Full article

The paradigm-shift idea of murburn concept is no hypothesis but developed directly from fundamental facts of cellular/ecological existence. Murburn involves spontaneous and stochastic interactions (mediated by murzymes) amongst the molecules and unbound ions of cells. It leads to effective charge separation (ECS) and formation/recruitment of diffusible reactive species (DRS, like radicals whose reactions enable ATP-synthesis and thermogenesis) and emission of radiations (UV/Vis to ELF). These processes also lead to a chemo-electromagnetic matrix (CEM), ascertaining that living cell/organism react/function as a coherent unit. Murburn concept propounds the true utility of oxygen: generating DRS (with catalytic and electrical properties) on the way to becoming water, the life solvent, and ultimately also leading to phase-based macroscopic homeostatic outcomes. Such a layout enables cells to become simple chemical engines (SCEs) with powering, coherence, homeostasis, electro-mechanical and sensing–response (PCHEMS; life’s short-term “intelligence”) abilities. In the current review, we discuss the coacervate nature of cells and dwell upon the ways and contexts in which various radiations (either incident or endogenously generated) could interact in the new scheme of cellular function. Presenting comparative evidence/arguments and listing of systems with murburn models, we argue that the new perceptions explain life processes better and urge the community to urgently adopt murburn bioenergetics and adapt to its views. Further, we touch upon some distinct scientific and sociological contexts with respect to the outreach of murburn concept. It is envisaged that greater awareness of murburn could enhance the longevity and quality of life and afford better approaches to therapies. Full article

Catalytic upgrading of pyrolysis oils is an important step for producing replacement hydrocarbon-rich liquid biofuels from biomass and can help to advance pyrolysis technology. Catalysts play a pivotal role in influencing the selectivity of chemical reactions leading to the formation of main compounds in the final upgraded liquid products. The present work involved a systematic study of solvent-free catalytic reactions of cyclohexanone in the presence of hydrogen gas at 160 °C for 3 h in a batch reactor. Cyclohexanone can be produced from biomass through the selective hydrogenation of lignin-derived phenolics. Three types of catalysts comprising undoped NbOPO₄, 10 wt% NiO/NbOPO₄, and 30 wt% NiO/NbOPO₄ were studied. Undoped NbOPO₄ promoted both aldol condensation and the dehydration of cyclohexanol, producing fused ring aromatic hydrocarbons and hard char. With 30 wt% NiO/NbOPO₄, extensive competitive hydrogenation of cyclohexanone to cyclohexanol was observed, along with the formation of C₆ cyclic hydrocarbons. When compared to NbOPO₄ and 30 wt% NiO/NbOPO₄, the use of 10 wt% NiO/NbOPO₄ produced superior selectivity towards bi-cycloalkanones (i.e., C₁₂) at cyclohexanone conversion of 66.8 ± 1.82%. Overall, the 10 wt% NiO/NbOPO₄ catalyst exhibited the best performance towards the production of precursor compounds that can be further hydrodeoxygenated into energy-dense aviation fuel hydrocarbons. Hence, the presence and loading of NiO was able to tune the activity and selectivity of NbOPO₄, thereby influencing the final products obtained from the same cyclohexanone feedstock. This study underscores the potential of lignin-derived pyrolysis oils as important renewable feedstocks for producing replacement hydrocarbon solvents or feedstocks and high-density sustainable liquid hydrocarbon fuels via sequential and selective catalytic upgrading. Full article

Biocatalysis is one of the oldest fields that has been used in industrial applications, with one of the earliest purposeful examples being the mass production of acetic acid from an immobilized Acinetobacter strain in the year 1815. Efficiency, specificity, reduced reaction times, lower overall costs, and environmental friendliness are some advantages biocatalysis has over conventional chemical synthesis, which has made biocatalysis increasingly used in industry. We highlight three necessary fields that are fundamental to advancing industrial biocatalysis, including biocatalyst engineering, solvent engineering, and mechanistic engineering. However, the fundamental mechanism of enzyme function is often overlooked or given less attention, which can limit the engineering process. In this review, we describe how mechanistic enzymology benefits industrial biocatalysis by elucidating key fundamental principles, including the k_cat and k_cat/K_m parameters. Mechanistic enzymology presents a unique field that provides in-depth insights into the molecular mechanisms of enzyme activity and includes areas such as reaction kinetics, catalytic mechanisms, structural analysis, substrate specificity, and protein dynamics. In line with the objective of protein engineering to optimize enzyme activity, we summarize a range of strategies reported in the literature aimed at improving the product release rate, the chemical step of catalysis, and the overall catalytic efficiency of enzymes. Further into this review, we delineate kinetic solvent viscosity effects (KSVEs) as a very efficient, cost-effective, and easy-to-perform method to probe different aspects of enzyme reaction mechanisms, including diffusion-dependent kinetic steps and rate-limiting steps. KSVEs are cost-effective because simple kinetic enzyme assays, such as the Michaelis–Menten kinetic approach, can be combined with them without the need for specialized and costly equipment. Other techniques in protein engineering and genetic engineering are also covered in this review. Additionally, we provide information on solvent systems in enzymatic reactions, details on immobilized biocatalysts, and common misconceptions that misguide enzyme design and optimization processes. Full article

Interfacial polymerization (IP) has been widely utilized to synthesize composite membranes. However, precise control of this reaction remains a challenge due to the complexity of the IP process. Herein, an optical three-dimensional microscope was used to directly observe the IP process. To construct copolyesteramide containing phthalazine moiety films, rigid monomer 4-(4′-hydroxyphenyl)-2,3-phthalazin-1-one (DHPZ) and flexible monomer piperazine (PIP) were used as aqueous phase monomers, and trimesoyl chloride (TMC) served as the organic phase monomer. Multilayer cellular structures were observed for the copolyesteramide films during the IP process. The effects of multiple factors including the ratio between flexible and rigid monomers, co-solvents, and the addition of phase transfer catalysts on the film growth and the morphologies were investigated. This research aims to deepen our understanding of the IP process, especially for the principles which govern polymer film growth and morphology, to promote new methodologies for regulating interfacial polymerization in composite membrane preparation. Full article

The sustainable recovery of valuable metals such as Cu and Co from ores is a pressing need considering environmental and economic challenges. Therefore, this study evaluates the effectiveness of deep eutectic solvents (DESs) as alternative leaching agents for Cu and Co extraction. Four DESs were prepared using choline chloride (ChCl) as a hydrogen bond acceptor (HBA) and oxalic acid (OA), ethylene glycol (EG), urea (U) and thiourea (TU) as hydrogen bond donors (HBDs). Leaching experiments were conducted with DESs supplemented with 30 wt.% water at varying temperatures, various solid-to-liquid ratios, and time durations. The ChCl:OA DES demonstrated the highest leaching efficiencies among the DESs tested on pure CuO and CoO, achieving 89.2% for Cu and 92.4% for Co (60 °C, 400 rpm, 6 h, −75 + 53 µm particle size, and 1:10 solid-to-liquid ratio). In addition, the dissolution kinetics, analysed using the shrinking core model (SCM), showed that the leaching process was mainly controlled by surface chemical reactions. The activation energy values for Cu and Co leaching were 46.8 kJ mol⁻¹ and 51.4 kJ mol⁻¹, respectively, supporting a surface chemical control mechanism. The results highlight the potential of ChCl:OA as a sustainable alternative for metal recovery. Full article

Understanding the differential impacts of emission sources of volatile organic compounds (VOCs) on formaldehyde (HCHO) levels is pivotal to effectively mitigating key photochemical radical precursors, thereby enhancing the regulation of atmospheric oxidation capacity (AOC) and ozone formation. This investigation systematically selected and analyzed year-long VOC measurements across three urban zones in Shenzhen, China. Photochemical age correction methods were implemented to develop the initial concentrations of VOCs before source apportionment; then Positive Matrix Factorization (PMF) modeling resolved six primary sources: solvent usage (28.6–47.9%), vehicle exhaust (24.2–31.2%), biogenic emission (13.8–18.1%), natural gas (8.5–16.3%), gasoline evaporation (3.2–8.9%), and biomass burning (0.3–2.4%). A machine learning (ML) framework incorporating Shapley Additive Explanations (SHAP) was subsequently applied to evaluate the influence of six emission sources on HCHO concentrations while accounting for reaction time adjustments. This machine learning-driven nonlinear analysis demonstrated that vehicle exhaust nearly always emerged as the primary anthropogenic contributor in diverse functional zones and different seasons, with gasoline evaporation as another key contributor, while the traditional reactivity metric method, ozone formation potential (OFP), tended to underestimate the role of the two sources. This study highlights the primacy of strengthening emission reduction of transportation sectors to mitigate HCHO pollution in megacities. Full article

Hydrogen energy is a pivotal carrier for achieving carbon neutrality, requiring green and efficient production via water electrolysis. However, the anodic oxygen evolution reaction (OER) involves a sluggish four-electron transfer process, resulting in high overpotentials, while the prohibitive cost and complex preparation of precious metal catalysts impede large-scale commercialization. In this study, we develop a FeCo-based bimetallic deep eutectic solvent (FeCo-DES) as a multifunctional reaction medium for engineering a three-dimensional (3D) coral-like FeOOH-Co₂(OH)₃Cl/NF composite via a mild one-step impregnation approach (70 °C, ambient pressure). The FeCo-DES simultaneously serves as the solvent, metal source, and redox agent, driving the controlled in situ assembly of FeOOH-Co₂(OH)₃Cl hybrids on Ni(OH)₂/NiOOH-coated nickel foam (NF). This hierarchical architecture induces synergistic enhancement through geometric structural effects combined with multi-component electronic interactions. Consequently, the FeOOH-Co₂(OH)₃Cl/NF catalyst achieves a remarkably low overpotential of 197 mV at 100 mA cm⁻² and a Tafel slope of 65.9 mV dec⁻¹, along with 98% current retention over 24 h chronopotentiometry. This study pioneers a DES-mediated strategy for designing robust composite catalysts, establishing a scalable blueprint for high-performance and low-cost OER systems. Full article

Polycyclic aromatic compounds can often be made by a sequence featuring an initial Diels–Alder [4 + 2] cycloaddition reaction, followed by cheletropic extrusion of carbon monoxide. These reactions normally require heating the diene and dieneophile in petrochemical-derived aromatic hydrocarbon solvents, such as xylenes or diphenyl ether. This article summarizes the results of attempts to use renewable solvents in place of those currently in use to prepare pentaphenylbenzene and 1,2,4-triphenyltriphenylene. Dihydrolevoglucosenone, p-cymene, ethyl lactate, diethyl carbonate, and cyclopentyl methyl ether have all been successfully evaluated as renewable solvent alternatives in Diels–Alder/cheletropic reaction sequences. An analysis of the products from the reactions investigated did not show evidence of oxidative degradation of the diene reactants. Furthermore, norbornadien-7-one intermediates were not isolated from any of the reactions tested. Full article

In this work, we report a novel mechanochemical synthesis method for the synthesis of quinoxaline derivatives—a spiral gas–solid two-phase flow approach, which enables the efficient preparation of quinoxaline compounds. Compared to conventional synthetic methods, this approach eliminates the need for heating or solvents while significantly reducing reaction time. The structures of the synthesized compounds were characterized using nuclear magnetic resonance (NMR), Fourier-transform infrared spectroscopy (FT-IR), ultraviolet-visible (UV–Vis) absorption spectroscopy, powder X-ray diffraction (XRD), differential scanning calorimetry (DSC), and high-performance liquid chromatography (HPLC). Using the synthesis of 2,3-diphenylquinoxaline (1) as a model reaction, the synthetic process was investigated with UV–Vis spectroscopy. The results demonstrate that when the total feed amount was 2 g with a carrier gas pressure of 0.8 MPa, the reaction completed within 2 min, achieving a yield of 93%. Furthermore, kinetic analysis of the reaction mechanism was performed by monitoring the UV–Vis spectra of the products at different time intervals. The results indicate that the synthesis of 1 follows the A4 kinetic model, which describes a two-dimensional diffusion-controlled product growth process following decelerated nucleation. Full article

This study systematically investigated the oxidation of chitosan using the TEMPO/NaClO/NaBr catalytic system under varying experimental conditions, namely temperature, reaction time, and pH, in order to optimize the oxidation process. Response surface methodology (RSM) was employed to determine the optimal parameters for maximizing the efficiency of the reaction. The structural modifications to the chitosan following oxidation were confirmed using Fourier-transform infrared spectroscopy (FTIR), alongside additional analytical techniques, which validated the successful introduction of carbonyl and carboxyl functional groups. Solvent-cast films were prepared from both native and oxidized chitosan in order to evaluate their functional performance. The antibacterial activity of these films was assessed against Gram-negative (Salmonella) and Gram-positive (Streptococcus faecalis) bacterial strains. The oxidized chitosan films exhibited significantly enhanced antibacterial effects, particularly at shorter incubation periods. In addition, antioxidant activity was evaluated using DPPH radical scavenging and ferrous ion chelation assays, which both revealed a marked improvement in radical scavenging ability and metal ion binding capacity in oxidized chitosan. These findings confirm that TEMPO-mediated oxidation effectively enhances the physicochemical and bioactive properties of chitosan, highlighting its potential for biomedical and environmental applications. Full article

Poor aqueous solubility still disqualifies many promising drug candidates at late stages of development. Amorphous solid dispersion (ASD) technology solves this limitation by trapping the active pharmaceutical ingredient (API) in a high-energy, non-crystalline form, yet most marketed ASDs rely on synthetic carriers such as polyvinylpyrrolidone (PVP) and hydroxypropyl methylcellulose (HPMC), which raise concerns about long-term biocompatibility, residual solvent load, and sustainability. This study summarizes the emergence of natural polymer-based ASDs (NP-ASDs), along with the bond mechanism reactions through which these natural polymers enhance drug performance. As a result, NP-ASDs exhibit improved physical stability and significantly enhance the dissolution rate of poorly soluble drugs. The structural features of natural polymers play a critical role in stabilizing the amorphous state and modulating drug release profiles. These findings support the growing potential of NP-ASDs as sustainable and biocompatible alternatives to synthetic carriers in pharmaceutical development. Full article

The development of ceria (CeO_2−x)-based nanoantioxidants requires fine-tuning of structural and surface properties for enhancing antioxidant behavior in biological environments. In this contest, here ultrasmall water-dispersible CeO_2−x nanoparticles (NPs), characterized by a high Ce³⁺/Ce⁴⁺ ratio, were synthesized in a non-polar solvent and phase-transfer to an aqueous environment through ligand-exchange reactions using citric acid (CeO_2−x@Cit) and post-treatment with dopamine hydrochloride (CeO_2−x@Dopa). The concept behind this work is to enhance via surface engineering the intrinsic antioxidant properties of CeO_2−x NPs. For this purpose, thanks to electron transfer reactions between dopamine and CeO_2−x, the CeO_2−x@Dopa was obtained, characterized by increased surface Ce³⁺ sites and surface functionalized with polydopamine bearing o-quinone structures as demonstrated by complementary spectroscopic (UV–vis, FT-IR, and XPS) characterizations. To test the antioxidant properties of CeO_2−x NPs, the scavenging activity before and after dopamine treatment against artificial radical 1,1-diphenyl-2-picrylhydrazyl (DPPH^·) and the ability to reduce the reactive oxygen species in Diencephalic Immortalized Type Neural Cell line 1 were evaluated. CeO_2−x@Dopa demonstrated less efficiency in DPPH^· scavenging (%radical scavenging activity 13% versus 42% for CeO_2−x@Cit before dopamine treatment at 33 μM DPPH^· and 0.13 mg/mL loading of NPs), while it markedly reduced intracellular ROS levels (ROS production 35% compared to 66% of CeO_2−x@Cit before dopamine treatment with respect to control—p < 0.001 and p < 0.01, respectively). While steric hindrance from the dopamine-derived polymer layer limited direct electron transfer from CeO_2−x NP surface to DPPH^·, within cells the presence of o-quinone groups contributed with CeO_2−x NPs to break the autoxidation chain of organic substrates, enhancing the antioxidant activity. The functionalization of NPs with o-quinone structures represents a valuable approach to increase the inherent antioxidant properties of CeO_2−x NPs, enhancing their effectiveness in biological systems by promoting additional redox pathways. Full article

Human applications of surfactants have been diverse, from their initial use as detergents to their subsequent utilization in a multitude of other fields, including medicine, lubricants, cosmetics, and even assisted oil recovery. Nevertheless, the most significant challenge lies in the synthesis of surfactants. A particular challenge is the purification of compounds following chemical synthesis, as well as the toxic effect of the solvents used. Consequently, there is a growing need for more environmentally friendly solutions, namely solvents that are less toxic and more biocompatible, as well as reactions in which an enzyme serves as a catalyst. This review examines the various methods of synthesizing sugar esters and glycolipids, evaluating their respective advantages and disadvantages. Full article

Poly(acrylic acid) (PAA) and hydroxypropylcellulose (HPC) hydrogels were synthesized in the absence of a crosslinker. Chemical crosslinking between PAA and HPC was demonstrated through free radical polymerization by a precipitation reaction in acetone as the solvent. These hydrogels exhibited smaller swelling ratios (1 to 5 g H₂O/g) than homo PAA hydrogels synthesized in water as the solvent. They were swollen in a 0.1 M NaOH solution and subsequently used to remove Ni²⁺ ions from aqueous solutions with concentrations ranging from 1000 to 4000 ppm. The absorption capacity of these hydrogels ranged from 91 to 340 mg of Ni²⁺/g in a rapid 1 h process, and from 122 to 435 mg of Ni²⁺/g in a 24 h process, demonstrating an improvement in Ni²⁺ absorption compared to previously reported hydrogels. The colored 1000 and 2000 ppm Ni²⁺ solutions became clear after treatment, while the PAA-HPC hydrogels turned green due to the uptake of Ni²⁺ ions, which were partially chelated by carboxylate groups as nickel polyacrylate and partially precipitated as Ni(OH)₂, resulting in an average absorption efficiency of 80%. The hydrogel was able to release the absorbed Ni²⁺ upon immersion in an HCl solution, with an average release percentage of 76.4%, indicating its potential for reuse. These findings support the use of PAA-HPC hydrogels for cleaning Ni²⁺-polluted water. The cost of producing 1 g of these hydrogels in laboratory conditions is approximately 0.2 USD. Full article